Reaction products of copper and mercury salts and process for rendering cotton fabric rot resistant therewith



United States Patent 3,291,635 REACTION PRODUCTS OF COPPER AND MER- CURYSALTS AND PROCESS FOR RENDERING COTTON FABRIC ROT RESISTANT THEREWITHCharles J. Conner, New Orleans, La., assignor to the United States ofAmerica as represented by the Secretary of Agriculture No Drawing. FiledApr. 2, 1964, Ser. No. 356,991 16 Claims. (Cl. 117-1385) A nonexclusive,irrevocable royalty-free license in the invention herein described,throughout the world for all purposes of the United States Government,with the power to grant sublicenses for such purposes, is hereby grantedto the Government of the United States of America.

This application is a continuation-in-part of Serial No. 253,232, filedJanuary 22, 1963, now US. Patent 3,183,- 118.

This invention relates to the formation, and subsequent deposition oncotton fabrics of complex water soluble derivatives, which are preparedby solubilizing copper and mercury salts, that are normally waterinsoluble, with zirconyl ammonium carbonate. Whereas Serial No. 253,232relates to the water solubilizing of certain normally water insolublecopper and mercury salts via chemical reaction with zirconyl acetate toproduce specific agents for textile treatment, the presentcontinuationin-part application relates to derivatives produced by thechemical reaction of zirconyl ammonium carbonate (ammonium zirconylcarbonate) with certain normally water insoluble chemical compounds, ofcopper and mercury to the end that water soluble agents suitable fortextile treatment are produced,

By process of this invention a copper borate and other water insolublesalts are made water soluble by treatment with zirconyl ammoniumcarbonate solutions. This treatment produces in the case of copper, adeep blue water soluble complex substance which can be later decomposedto form a derivative which is insoluble in water. Generally, the copperand mercury salts are easily and adequately soluble for use in treatingtextiles only in organic solvents, or they require solvent-emulsionsystems for utilization.

Utility of water insoluble fungistatic and fungicidal agents is enhancedby the process of this invention in that the derivatives formed arewater soluble, thereby making their commercial application moreeconomical. Zirconyl ammonium carbonate has been used in textiletreatments to produce water repellency in wax emulsions (Industrial andEngineering Chemistry, vol. 42, page 640, April 1950). Certain coppercompounds have long been used as fungicidal textile treatments but theirapplication has been limited by the necessity of application fromorganic solvents or emulsion systems (Fungusproofing of Textiles andCordage for Use in Tropical Service, Office of Scientific Research andDevelopment Report No. 4513, January 1945). Obviously, the use of watersoluble chemicals reduces the cost of treatments.

The preferred concentration of zirconium oxide in the zirconyl ammoniumcarbonate solutions is about from 0.25% to 10.00%, calculated as ZrOThese concentrations are ideal for the dissolution and com-plexing ofthe copper and mercury compounds in the zirconyl ammonium carbonatesolutions. These deep blue copper complex solutions can be furthersolubilized in water, and have been prepared at concentrations aboutfrom 0.1% to 35% total solids, the blue coloration being visible at 'iceall concentrations. The mercury complex solutions are colorless, andhave been prepared at concentrations about from 0.1% to 38.4% totalsolids.

Fungicidal activity has 'been established for both zirconium and themetal salts by Sin, Microbial Decomposition of Cellulose, ReinholdPublishing Corp, New York 1951, and the particular derivatives producedby process of this invention likewise have this quality. Algaecidalactivity of zirconium has been noted by Conner, Cooper, Reeves, andTrask and reported in Some Microbial Resistant Compounds of Zirconiumand Their Effect on Cotton (in manuscript). These water solublecompositions undergo a chemical change when heated, as indicated below,and this change is made manifest by the fact that the water solublesubstance becomes insoluble when heated above a particular criticaltemperature, as based on the known mechanisms for zirconyl ammoniumcarbonate alone:

Note: The rate of decomposition is much faster when higher temperaturesare employed (Ref.: Titanium Alloy Mfg. Division, Data File D-52,5/28/59).

When a copper or mercury complex exists in the aqueous phase withzirconyl ammonium carbonate, decomposition by heating effectivelyresults in precipitation of ZrO with the mercury or copper derivative asan insoluble residue. CO and NH are lost during the decomposition.

Other water soluble compositions capable of being prepared by the actionof zirconyl ammonium carbonate solution upon the water insoluble saltsof the heavy metals include compositions prepared from the followingmercury salts:

Phenyl Mercury Acetate Phenyl Mercury Salicylate Phenyl Mercury LactatePhenyl Mercury Propionate Phenyl Mercury Borate Phenyl Mercury BenzoateAll the water soluble compositions prepared from the above listed salts,as well as those prepared from their homologs, can be applied to cottonto produce materials with fungistatic or fungicidal properties.

A suitable copper borate for solubilization is one containing a CuO to B0 molar ratio about from 2:3 to 1:2. The copper borate may be hydratedor anhydrous. The appropriate zirconyl ammonium carbonate solutions areavailable commercially, zirconyl ammonium carbonate solution suitablefor the purpose of this invention is one having the followingspecifications:

ZrO percent by weight 10.0 Molecular wt. of solute 378.39 Density ofsolution at 24 C. 1.238 pH at 24 C. 9.6

The reactants have the following formulae:

Zirconyl ammonium carbonate Copper borate Note: x and y represent molarratios.

Phenyl mercury acetate (representative of phenyl mercury salts) Thesolubility of phenyl mercury salts in zirconyl ammonium carbonatesolution (10% ZIO2) is complete up to 4.0% mercury and 95% soluble up to4.24% mercury. The phenyl mercury acetate and propionate are completelysoluble up to 4.1% mercury. The copper borate (1 CuO:2B O is soluble tothe extent of 4% in the zirconyl ammonium carbonate (10% ZrO When anaqueous solution of the copper borate complex is evaporated to dryness,a blue insoluble granular compound is formed. This compound shows noevidence of solubility in water when washed and extracted with distilledwater.

One explanation of the mechanisms involved in the preparation of thesesubstances is here exemplified:

Copper borate-Zirconyl ammonium carbonate derivative (water soluble)theoretical molecular weight 833.88

In the case of phenyl mercury salts, i.e., acetate, the mechanism can beexplained as follows:

In the case of decomposition of these complexes with heat the mechanismcan be explained as follows:

The insoluble derivative from heat decomposition is blue-green and showsstrong afiinity for cellulose, resisting four hours of water leachingwithout evidence of loss of material through solubility. The possibilityof crosslinkage of zirconium compounds with cellulose is known, and thefollowing suggested structure could explain the heat-decomposed copperborate-zirconyl ammonium carbonate residual:

insol. compd. CUBzOA- (ZI'Oz) z ZHaO HOBOZ"r-OH Insoluble (deposit fromcopper borate-zlrconyl ammonium complex decomposition) The heatdecomposition mechanism for aqueous phenyl mercury salt-zirconylammonium carbonate complexes may be explained according to the followingcomplex with phenyl mercury acetate:

The relative insolnbility of the deposit, as compared with phenylmercury acetate alone, in conjunction with a strong afiinity forcellulose, suggests the following structure for the insoluble residue:

OH O

2.0 grams ofthe borate will complex with 15.6 grams of zirconyl ammoniumcarbonate from calculation) or to the extent of 2.0% copper borate, byreacting at room temperature over a period of 48 hours. Time offers nodifiiculty, since the copper borate is allowed to macerate withoccasional agitation over this period, and any quantity may be preparedat one time.

Aqueous padding solutions useful for application to cotton as afungicide have been found to be preferably stable at room temperatures(about 25 C.) for several weeks. These solutions can be stableindefinitely as long as an upper temperature limit of 50 C. is avoided.Past this upper limit the ingredients become insoluble, which featurebecomes an asset in that cotton fabrics treated with the solutions andsubsequently cured past the upper limit will acquire and retainfungistatic properties which are stable through launderings and exposureto weather.

The water soluble composition of copper borate-zirconyl ammoniumcarbonate has been applied from solids concentrations with as low as0.425% Cu and 2.50% ZrO to cotton cloth (army duck), to produce a gooduniform application on the padder, and further cured on the cloth attemperatures about from 100 to 145 C., producing an insoluble blue-greendeposit, which contains 0.2% Cu and 1.25% ZrO which deposit withstands a4-hour water leaching test without loss. The deposit on the clothpossesses inherently qualities of high fungistatic and fungicidalactivity, since it contains three known elements of noted fungicidalactivity, i.e., copper, zirconium, and boron.

A sample of cloth treated and cured as described above, and having a0.4% Cu and 2.50% Zr add-on, was buried in a composted soil bed togetherwith an untreated control sample and exposed to microbiological attackfor 7 days. Subsequently both samples were removed, and tested forbreaking strength. The treated cloth retained 100% of its originalstrength, while the untreated control had practically disintegrated andretained only 7% of its original strength. Another quality of the clothtreated by the process of this invention is notable water repellency.

Water soluble compositions of phenylmercury salts and zirconyl ammoniumcarbonate have been applied from solids concentration with as low as0.5% Hg and 2.50% ZrO where the cloth add-on was 0.25% Hg and 1.25% ZrOArmy duck, so treated, received a good, uniform add-on when padded andcured (put in oven while wet) 5 minutes at 145 C. The treatment produceda colorless, insoluble deposit, which withstood a 4-hour water leachingtest without loss. The deposit on the cloth possesses high fungistaticand fungicidal activity, since it contains the elements of knownfungicidal activity, i.e., mercury and zirconium.

Samples of cloth treated and cured as described above, and having a 0.4%Hg and 2.40% Zr0 add-on, were buried in a composted soil bed togetherwith an untreated control and exposed to microbiological attack for 42days. Samples of each were periodically removed, and tested for breakingstrength. The treated cloth retained 100% of its original strength after42 days exposure, While the untreated cloth retained only 7% of itsoriginal strength at the end of 7 days exposure and was completelydisintegrated at the end of the 14th day.

The phenyl mercury acetate and lactate derivatives with zirconylammonium carbonate deposited on duck showed 100% retained breakingstrength at the end of 28 days of exposure to microbiological attack(burial in the composted bed). Again, it was noted that heat cureddeposits of these phenylmercury-zirconyl ammonium carbonate derivativesproduce notable water repellency characteristics on cotton cloth.

The following examples are specific cases set forth to illustrate theinvention in detail, and percentages are by weight.

Example 1 1.0 gram of copper borate (1 CuO:2B O anhydrous salt and 50grams of zirconyl ammonium carbonate solution ZrO in water were mixedand allowed to stand for 48 hours at room temperature (25 C.), withoccasional agitation. At the end of this time, all of the copper boratehad dissolved to produce a dark blue solution of the water solublecomposition formed.

Example 2 1.0 gram of copper borate (1 CuO:2B O hydrated (2H O) salt and50 grams of zirconyl ammonium carbonate solution (10% ZrO in Water weremixed and allowed to stand for 48 hours at room temperature (25 C.),with occasional agitation. At the end of this time all of the copperborate had dissolved to produce a dark blue solution of the watersoluble composition formed.

Example 3 2.0 grams of copper borate (1 CuO:2B O hydrated (21-1 0) saltand 50 grams of zirconyl ammonium carbonate solution (10% ZrO in waterwere mixed and allowed to stand for 48 hours at room temperature (25C.), with occasional agitation. At the end of this time all of thecopper borate had dissolved to produce a dark blue solution with a traceof sediment. This solution, containing 1.70% Cu, was diluted with 150grams water to produce a 0.42% Cu content. Fifty grams of this solutionwere diluted with 250 grams of water to produce a 300 gm. solutioncontaining .07% Cu and 0.2% ZrO This solutioin was diluted with an equalweight of water to give a solids of 0.135 A blue color was stillnoticeable and the solution remained clear.

Example 4 1.0 gram of copper borate (2 CuO:3B O anhydrous salt and 50grams of zirconyl ammonium carbonate solution (10% ZrO in water weremixed and allowed to stand for 48 hours at room temperature (25 C.),with oc casional agitation. At the end of this time, all of the copperborate had dissolved to produce a dark blue solution. The solution washeated to about 55 C. for one hour. Evidence of dissociation was notedwith slight ppt. formation. When heated to C., for 5 minutes, a blueprecipitate formed, showing complete dissociation at this temperature,resulting in precipitation of the copper and zirconium ion. The filteredppt. was not soluble in distilled water.

Example 5 Two grams of copper borate (1 CuO-2B O hydrated (2H O) saltand 50 gins. of zirconyl ammonium carbonate solution (10% ZrO in waterwere mixed and allowed to stand and macerate for 48 hours at roomtemperature (25 C.), with occasional agitation. At the end of this time,all of the copper borate had dissolved to produce a dark blue solutionwith a trace of sediment. This solution, contaiinng 1.70% Cu and 10% ZrOwas diluted with 50 gms. of distilled water to produce a dark bluesolution containing 0.85% Cu and 5% ZrO This solution was used to pad 8oz. army duck, using two nips and dips, and passed through tight rollsto give a wet pickup of 50%, equivalent to 0.42% Cu and 2.50% ZrO Thewet treated cloth had a pale blue color. Cure was effected at C. for 5minutes in an electric oven. The cloth developed a pale blue-greencolor, as a result of the deposition of copper and zirconium ions ontothe cloth, as an insoluble compound. Color of the treatment was uniformand not objectionable. Samples of the cured treated cloth were leachedfor 1 hour with tap water, while others were leached for 4 hours withdistilled water. No evidence of loss of treatment through color loss wasnoted with either leaching procedure and resistance to Wetting wasnotable. The in situ change from the soluble derivative to the insolublederivative requires that curing temperature be 145 C. for a 5-minutecuring time. Lower temperatures would naturally require a longer timeinterval.

A section of the cured treated cloth was cut into 5 strips of cloth, 1inch by 7 inches each, and 5 strips were cut from the untreated cloth,as ontrol. Both samples were buried in the rot bed (composted soil). Atthe end of a period of 7 days, the samples were dug up and examined.The'control samples were heavily mildewed and showed 7% retainedstrength. The treated samples showed no evidence of microbiologicalattack and retained 100% strength.

Example 6 The following three solutions of phenylmercury saltzirconylammonium carbonate compositions were prepared for padding onto duck (8oz.) and subsequent fungicide evaluation (soil burial test):

Solution A 5 gms. zirconyl ammonium carbonate solution (10% ZI'OZ) 1.7gms. phenyl mercury acetate 50 gms. distilled water Solution A contains1.0% Hg and 5% ZrO Solution B Solution C- 50 gms. zirconyl ammoniumcarbonate solution (10% 1.8 gms. phenyl mercury propionate 50 gms.distilled water Solution C contains 1.0% Hg and 5% ZrO These threesolutions were prepared by adding the zirconyl ammonium carbonatesolution to a weighed quantity of the appropriate phenyl mercury salt atroom temperature (25 C.) and warming the mixture to 40? C., Whilestirring, to effect rapid solubility. The prepared solutions were placedin stoppered containers and retained at room temperature (25 C.) priorto use as padding solutions. Samples of 8 oz. army duck (scoured) werepadded twice with the prepared respective solution on a conventionalpadder, followed by a direct cure at 145 C. for 5 minutes in an electricoven. Add-on (wet pickup of the fabric) was estimated at 49%, giving thetreated cloth a content of about 0.49% Hg. and about 2.45% ZrO Thetreated duck evidenced no loss in breaking strength when compared withan untreated control. At the end of 28 days in a soil (rot) bed, all ofthe treated samples showed 100% retained breaking strength, while thecomparative samples of untreated duck showed only 7% retained breakingstrength after one week, and complete disintegration at the end of twoweeks soil bed burial. At the end of 6 weeks soil bed burial, thepropionate derivative showed 100% retained breaking strength, theacetate derivative showed 77% retained breaking strength, and thelactate derivative showed 34% retained breaking strength.

Example 7 3.6 gms. of phenyl mercury propionate were dissolved in 100gms. of zirconyl ammonium carbonate solution ZrO- at 40 C., withstirring, to produce a clear solution. Three hundred grams of distilledwater were added to produce a clear solution containing 0.5% Hg and2.50% ZrO A sample of duck was padded with the solution to give a 50%add-on. The treated duck was then cured at 145 C. for 5 minutes toproduce a colorless fabric with good band. The theoretical add-ons of0.25% Hg and 1.25% ZrO were confirmed by X-ray fluorescence analyses.

Example 8 1.0 gram of copper borate (1 CuO'2B O anhydrous and 50 gramsof zirconyl ammonium carbonate solution (10% ZrO in Water are mixed andallowed to macerate for 48 hours in a stoppered flask. At the end ofthis time the copper borate has completely dissolved, and a dark 8 'bluesolution results. It contains 0.85% Cu and 10% ZrO or 2% copper borateand 10% ZrO The solution was emptied into an evaporating dish andevaporated to dryness on the hot plate. A dark blue, non-crystalline,water insoluble derivative remains.

Example 9 1.8 grams of phenyl mercury propionate and 50 grams ofzirconyl ammonium carbonate solution (10% ZrO in water were mixed atroom temperature (25 C.) and stirred. The phenyl mercury salt dissolvesto form a water soluble derivative containing 2.06% mercury and 10% ZrOThis was evaporated to dryness on the hot plate, resulting in ayellowish-white, non-crystalline, water insoluble derivative.

Example 10 Three samples of duck, which had been padded with a 1CuO-2B Ocopper borate-zirconyl ammonium carbon ate solution in water to give atheoretical add-on of 0.6% Cu and 5.0% ZIOZ, were analyzed (X-ray) forpercent Cu before water washing and after a 30 minute hot (50 C.) tapwater wash in one case, and 4 hours distilled water leaching in anothercase. The percent Cu was found to be 0.6% before wash, and 0.6% Cu after30 minutes hot tap water wash, and 0.6% Cu after 4 hours distilled waterleaching.

I claim:

1. A water soluble composition of copper borate and zirconyl ammoniumcarbonate having the formula:

2. A process for preparing a water soluble copper borate-zirconylammonium carbonate composition comprising mixing 2 to 4 parts by weightof copper borate with about 100 parts by weight of a solution ofzirconyl ammonium carbonate containing about 10% by Weight of Z'rO andabout by weight of Water, ammonia and carbon dioxide, and heating theresulting mixture at a temperature below 50 C. to dissolve the copperborate and produce the water soluble copper borate-zirconyl ammoniumcarbonate composition having the formula:

3. A Water insoluble composition of copper borate and zirconyl ammoniumcarbonate having the formula:

4. A process comprising heating to dryness the Water soluble compositionof copper borate and zirconyl ammonium carbonate having the formula:

at a temperature exceeding 50 C. to liberate carbon dioxide, ammoniagas, and water, and produce the water insoluble composition of copperborate and zirconyl am- 5 monium carbonate having the formula:

5. A process comprising heating to dryness the water soluble compositioncontaining copper and zirconium produced by the process of claim 2 at atemperature exceeding C. to liberate carbon dioxide, ammonium gas, andwater, and produce a water insoluble composition containing copper andzirconium.

6. A process for preparing a Water soluble composition containingmercury and zirconium comprising about from 1.7 to 1.9 parts by weightof a mercury compound selected from the group consisting of phenylmercuric acetate, phenyl mercuric lactate, and phenyl mercuricpropionate heating the resulting mixture at a temperature below 50 C. todissolve the mercury compound, and mixing the resulting solution with 50parts by weight of a solution of zirconyl ammonium carbonate containingfrom 5 to 10% by Weight of ZrO and from to by weight of water to producea water soluble composition containing mercury and zirconium.

7. The process of claim 6 wherein the mercury compound is phenyl mercuryacetate.

8. The process of claim 6 wherein the mercury compound is phenyl mercurylactate.

9. The process of claim 6 wherein the mercury compound is phenyl mercurypropionate.

10. A process comprising heating to dryness the water solublecomposition containing mercury and zirconium produced by the process ofclaim 7 at a temperature exceeding 50 C. to liberate carbon dioxide,ammonia gas, and water, and produce a Water insoluble compositioncontaining mercury and zirconium.

11. A process comprising heating to dryness the water solublecomposition containing mercury and zirconium produced by the process ofclaim 8 at a temperature exceeding 50 C. to liberate carbon dioxide,ammonia gas, and water, and produce a water insoluble compositioncontaining mercury and zirconium.

12. A process comprising heating to dryness the water solublecomposition containing mercury and zirconium produced by the process ofclaim 8 at a temperature exceeding 50 C. to liberate carbon dioxide,ammonia gas, and Water, and produce a water insoluble compositioncontaining mercury and zirconium.

13. A process for rendering cotton fabric rot resistant comprisingpadding the cotton fabric to a wet pickup of about 50% with an aqueoussolution containing the water soluble copper borate-zirconyl ammoniumcarbonate produced by the process of claim 2 dissolved therein in anamount corresponding to about 5% zirconium and about 0.85% copper toachieve an add-on of at least 2.5% zirconium by Weight and at least0.42% by weight of copper, and curing the padded fabric at a temperatureof about C. for a period of about 5 minutes, the shorter time intervalsbeing employed with the higher temperatures.

14. A process for rendering cotton fabric rot resistant comprisingpadding the cotton fabric to a wet pickup of about 50% with an aqueoussolution containing the water soluble phenyl mercury acetate-zirconylammonium carbonate produced by the process of claim 7 dissolved thereinin an amount sufficient to achieve an add-on of at least 0.49% by Weightof mercury and about 2.45% by weight of zirconium, and curing the paddedfabric at a temperature of about 145 C. for a period of about 5 minutes.

15. A process for rendering cotton fabric rot resistant comprisingpadding the cotton fabric to a wet pickup of about 50% with an aqueoussolution containing the water soluble phenyl mercury lactate-zirconylammonium carbonate produced by the process of claim 8 dissolved thereinin an amount suflicient to achieve an add-on of at least 0.49% by weightof mercury and about 2.45% by Weight of zirconium, and curing the paddedfabric at a temperature of about .145 C. for a period of about 5minutes.

16. A process for rendering cotton fabric rot resistant comprisingpadding the cotton fabric to a wet pickup of about 5 0% with an aqueoussolution containing the water soluble phenyl mercury propionate-zirconylammonium carbonate produced by the process of claim 9 dissolved thereinin an amount sufficient to achieve an add-on of at least 0.49% by Weightof mercury and about 2.45% by Weight of zirconium, and curing the paddedfabric at a temperature of about 145 C. for a period of about 5 minutes.

References Cited by the Examiner UNITED STATES PATENTS 2,482,816 9/1949Van Mater 117-121 2,698,263 12/1954 Weick 1l7138.5 3,183,118 5/1965Conner 117-138.5

MURRAY KATZ, Primary Examiner.

THEODORE G. DAVIS, Assistant Examiner.

2. A PROCESS FOR PREPARING A WATER SOLUBLE COPPER BORATE-ZIRCONYLAMMONIUM CARBONATE COMPOSITION COMPRISING MIXING 2 TO 4 PARTS BY WEIGHTOF COPPER BORATE WITH ABOUT 100 PARTS BY WEIGHT OF A SOLUTION OFZIRCONYL AMMONIUM CARBONATE CONTAINING ABOUT 10% BY WEIGHT OF ZRO2 ANDABOUT 90% BY WEIGHT OF WATER, AMMONIA AND CARBON DIOXIDE, AND HEATINGTHE RESULTING MIXTURE AT A TEMPERATURE BELOW 50*C. TO DISSOLVE THECOPPER BORATE AND PRODUCE THE WATER SOLUBLE COPPER BORATE-ZIRCONYLAMMONIUM CARBONATE COMPOSITION HAVING THE FORMULA:
 13. A PROCESS FORRENDERING COTTON FABRIC ROT RESISTANT COMPRISING PADDING THE COTTONFABRIC TO A WET PICKUP OF ABOUT 50% WITH AN AQUEOUS SOLUTION CONTAININGTHE WATER SOLUBLE COPPER BORATE-ZIRCONYL AMMONIUM CARBONATE PORDUCED BYTHE PROCESS OF CLAIM 2 DISSOLVED THEREIN IN AN AMOUNT CORRESPONDING TOABOUT 5% ZIRCONIUM AND ABOUT 0.85% COPPER TO ACHIEVE AN ADD-ON OF ATLEAST 2.5% ZIRCONIUM BY WEIGHT AND AT LEAST 0.42% BY WEIGHT OF COPPER,AND CURING THE PADDED FABRIC AT A TEMPERATURE OF ABOUT 145*C. FOR APERIOD OF ABOUT 5 MINUTES, THE SHORTER TIME INTERVALS BEING EMPLOYEDWITH THE HIGHER TEMPERATURES.